Preparation of titanium hydroxide



' Patented Mar. 29, 1932' UNITED STATES -PA EN.-'l o 1=1= "1c o'osnrn nnumnnrnnn, on runs, rn'ancn, nssrenon, BY mrsnn assrermnms, 'ro

' KBEIBS PIGMENT AND COLOB- CORPORATION, OF NEWARK, NEW JERSEY, A. COB- PORLTION OF DELAWARE rnnrnnarron or 'rrrmnm rrxnnoxinn No Drawing. iOriginal application filed February 2, 1928, Serial No. 251,258, now Patent No. 1,795,487, dated March 10,1931. Divided and this application filed May 15, 1930. Serial No. 452,812.-

This invention relates to a process for pre paring titanium hydroxide or oxide by thescribed by me in Patent 1,504,669. Solutions of this character usually contain iron and ma also contain various other impurities.

y proper chemical treatment the sulphuric acid solutions of titanium may be caused to undergo hydrolysis, with the resultant formation of aprecipitate of fre'eti- I an . tions of titanium oxide are brought to a pretanium hydroxide or oxide and an attend ant increase in theofree acidity of the solup tion. It should be noted, also, that the facts concerning the relation between titanium hydroxide and titanium dioxide are not completely known at the present time: Whentitanium solutions are treated chemically in a manner that should ordinarily produce a metallic hydroxide, the resultant product apparently undergoes a transition during drying and when fully dr is found to be titaniumdioxide (TiO ereafter, in the resent specification and claims, the hydro ysisproduct is referred to as titanium dioxide.

In existing hydrolysis processes the soluviously determined acid concentration and are then subjected to heating in various ways, such as boiling at atmospheric pressure or in autoclaves under elevated pressure, or in vacuo in some instances; the volume being maintained constant by refluxin or by adding fresh water. In all cases t e solutions subjected to hydrolysis are. true solutions and possess the homogeneity which characterizes crystalloid solutions.

. There is a wide variance in the physical and chemical properties of titanium dioxide produced by hydrolysis, dependent u on the exact conditions under which the hy rolysis takes place. The object of the present inven-;

tion is to'provide an improved hydrolysis process, whereby titanium dioxide of consistently uniform properties may beproduced rapidly and in good yield. Another object of the invention is to achieve this favorable result in a solutionof relatively high concentration, so that the sulphuric acid present and formed during the process may be recovered and concentrated economically. Other obects of the invention will become apparent. The invention consists in preparing titanium oxide,or hydroxide by hydrolyti'c recipitation, characterized by eflr'ecting the ydrolysis in a solution of titanium oxide in which a pronounced heterogeneity is created due to the presence therein of colloidal particles.

. The presence of iron in the solution to be hydrolyzed does not interfere with the reaction, but if much is present in solution it should be reduced, which may be accomsulphate, or by an improved rocess of refriggri'astion as described in my atent No. 1,707;

lished by. a simple crystallization of ferrous In order that the present invention may be appreciated, reference is made to an example showing a method of hydrolyzing in the ordinary way.

A solution of titanium containing about 200 grams per liter of TiO and 500 grams per.

litter of H 50 free or combined with titanium is diluted cold to a concentration of 400 grams per liter of H 80, and 160 ams per liter of TiO,,. This diluted SOllltlOlliS then heated to and maintained at a temperature of about 100 C. andgives by hydrolysis the very low yield of precipitated TiO of about 30%, the time taken to obtain this yield being about 24 hours. l

. 1 have now discovered that the speed of hydrolysis and quantitative yield of products may be increased and the quality of the precipitatedTiO may be im roved if the hy-j'eo drolysis of the titanium s phate solution is carried outin the presence of TiO in colloidal form. For example, if colloidal TiO is added to the solution to be hydrolyzed, which may be prepared as previously described, and exactly thesame method of hydrolysis is adopted,a yield of about TiO is obtained in about three hours. 7

To achieve'these favorable results one may either-add separately prepared colloidal titap 1928, now Patent No. 1,795,467, dated Marchnium dioxide to the solution prior to hydrolysis, or one may conduct the hydrolysis itself m such a :manner that an adequate quantity of colloidal TiO is produced inthe solution prior-to any actual precipitation if Ti(). This application is a division of-my application Serial No. 251,253, filed February 2,

10, 1931, and a continuation-of my application Serial No. 128,324, filed August 9, 1926, and

.relatesparticularly to the first of these two liter of H (free and combined with titatrationof colloidal crease. Y

The solutionrich in colloidal T210 producedas described above and before any subnium) to a greater quantity of boiling water. The solution is added at a uniform rate over a period equivalent to about 4 to 6 minutes per volume of solution added to a volume of water and the mixture is stirred during the addition. I I

As the two solutions are mixed, colloidal TiO will be formed and the concentration of the colloidal TiO will continue to increase after the mixing is completed. After a short time, however, TiO will commence to precipitate out of the solution and the concen- TiO will thereafter destantial precipitation of TiO may be mixed 4 with a titanium solution containing about 200 grams of TiO perliter and 500 grams of 1 H SO per liter in such proportions that the mixed solutions will have an H2804 concentration (free and combined with titanium) of about 400 grams per liter. These mixed solutions may be heated to about the boiling temperature for approximately three hours to complete the hydrolysis.

If preferredthe collodial suspension of TiO may be produced in a more concentrated titanium sulphate'solution by using a smaller quantity ofv water. In this event the solution to be hydrolyzed should be diluted in order that the resultant mixture may have the desired H SO concentration. For example, if the solution containing the colloidal TiO has an acid concentration of about 400 grams per liter, it may be added to a solution to be hydrolyzed which contains about 400 grams per of H and 160 grams per liter of If the solution of colloidal TiO is to be kept for some time, it may be stabilized by may be stabilized and store for use as needed.

being cooled when it has reached the maximum concentration of colloidal particles and before any active precipitation has taken 7 place. In this manner large quantities of the v colloidal TiO solutions ma be prepared and The solution containing the colloidal T10 produced as described above will I pass I through a filter and theconcentration of colloidalvTiO in the solutionsmay be determined by filtering the solution, coagulating the colloidal TiO in the filtrate and filtering out and weighing the coagulated TiOg.

The coagulation of the colloidal TiO may be accomplished by adding concentrated hydrochloric acid to the'solution and boiling.

The titanium dioxide produced by my hydrolysis process is removed from themixture by decantation and/or by filtering, after which it may be washed to remove acid and iron, and is dried. The dry TiO may be treated in various ways depending upon how it is to be used. For the preparation of pigment, it may be calcined in the manner usual 1y employed in preparing pigments. The re- 9c sultant product is a tough granular material which may be converted into an excellent white pigment by grinding.

I have found that it is the presence ofcolloidal TiO in the mixture that causes the improved yield and rate of hydrolysis, but the exact manner in which the colloidal phase promotes the precipitation is not known. The concentration of the colloidal TiQ in the solution to be hydrolyzedmay be varied between wide limits, for example, a I great improvement in the results maybe had with a concentration of colloidal TiO as'low as-l A or 2 grams per liter and concentrations up to and considerably above 30 grams per liter may be used. Both the final yield of TiO from hydrolyv sis and the quality of the material for-.pig-

-ment purposes, after calcining, is afi'ected'by the final acidity of the solution hydrolyzed, I

In turn, the final acidity is, of course, an expression of the concentration at which the A hydrolysis is effected. The proportions of acid to TiO given in the examples'have been used because they represent the solutions ordinarily obtained in the treatment of titanium-bearing ores (ilmenite), but hydrolysis can be performed with equal satisfaction in solutions having a greater or less free acidity factor than those given in the examples.

Much more important than the free acidity factor is the total or final acidity of-the hydrolyzed solution expressed as-sulphuric acid. This acidity will be equal to the free acid originally present prior to hydrolysis, plus the acid liberated during the hydrolysis as the result of the precipitation of TiO This final acidity should be in'the neighborhood of 400 grams per liter, since the best recovery of the -TiO is obtained at this conof the strong solution, weak solution and' centration, although the process is operable at lowerconcentrations. On the contrary, itis not advisable to operate the process at acid concentrations much above 400 grams per liter because of the tendency of-the TiO to re-dissolve in the acid present. Ifthe acid is too concentrated, theyields are low, while if'it is too dilute, the process is uneconomic and gives a poor product.

The final acidity of the hydrolysis mixture is, of course, independent of the precise y quantities of titanium solution and water mixed, and the desired final concentration may be had bymixing different quantities of solutions of the concentration available, the final concentration depending upon the ratio water.

Titanium solutions originally containing considerably less than 600 grams per liter of sulphuric acid may be hydrolyzed in accordance with my process. In general, more dilute solutions are more easily hydrolyzed and at lower temperatures. On adding a small quantity of such solutions to hot water,

colloidal TiO is formed in the same manner,

- the loss of titanium in the plant may be avoided. Satisfactory results ma also be obtained with water or dilute solution which are not heated to the boiling temperature as described in the example.

The process can be applied not only to the hydrolysis of titanium solutions but to other.

hydrolyzable solutions such as those of zirconium, thorium, tin, cerium, etc., and further these methods are equally valid when the precipitation is eifected in the presence of other substances adapted to serve, for .ex-

ample, as constituents 'o paint pigments, etc.

(such as B1150 CaSO,,' SiO and the'ilike) with which it is de'siredto mixthe' m'ain'precipitate very intimately. These substances may either be prepared in the same apparatus in which the hydrolysis takesplace, or separately. I

' It is apparent that many modifications of my invention may beutilizedandit is not intendedto limit the invention to the parti'cu--.

lar illustrations giyen;

What 'I claim-is;

1. In thelpreparati'on of 'titanium'oxide,-or:

' sulphate e production of colloidal particles titanium sulphatean'd heatin the mixed s0- lutlons to complete the precipitation.

2. Inthe preparation oftitanium' oxide, or

hydroxide, the steps comprising mixing a separately prepared colloidal solutionof ti-i tamum dioxide with a solution containing hydroxide, the steps comprising mixing a separately prepared solution containing colloidal titanium oxide or hydroxide with a solution containing titanium and sulphate ions, and heating the mixed solutions.

3. In the preparation oftitanium oxide,

or hydroxide, the stepscomprising mixing a I -separately prepared diluent and colloidal titanium-oxide or hydroxide with a solution.

containing titanium and sulphate ions, and heating during the precipitation.

4. In the preparation of titanium oxide, or hydroxide, the steps comprising mixing a separately prepared solution containing 001- loidal titanium dioxide orhydroxide with a crystalloid solution containing titaniumand tation.

.5. 'In the preparation the'steps comprising mixing'a separately prepared solution containing. colloidal titanium dioxide with a solution'containing titanium sulphate and heating the mixed solutions .to

substantially the boiling temperature.

the steps comprising mixing a separately prepared solution containing colloidal titanium oxideor' hydroxide with a titanium sulphate solution in such proportions that the, result a'nt solution will have a' concentration of sul-' phuric acid, free and combined with titanium,

of about 400 grams mixed solutions.

7 In the preparation of titanium dioxide,

o ftitanium dioxide,

ions, and heating during the precipi i 6. In the preparation of titanium dioxide,

per liter, and heating the V the steps comprising mixing a separately prepared solution containing colloidal titaniumoxide or. hydroxide with-atitanium sulphate solution in the presence of a substance adapted toserve as'a constituent of a paint pigment and heating the mixed solutions;

8. In the preparation of an oxide ofone of the elements of the titanium-thorium group,

the steps comprising mixing a separately prepared solution containing a colloidal suspension of the oxide of the' element with a solutioncontaining a sulphate of the element,

and heating the mixed solutions.

9. In'the preparation oi'za stable solution containing colloidal titanium dioxide, the";

.. steps comprising adding a concentrated solution'of .titaniumwsu'lphate to hot water and coolingthe-mixed solution before anysub stantial precipitation of titanium dioxide takes place. v

lOiiA'stable'solution containing colloidal titanium dioxide in the presence oftitanium' I and sulphate ions.

. .11. A solution containing colloidal titanium dioxide capable of being coagulated by boiling with hydrochloric acid.

12. In the preparation of an oxide of one of the elements of the group comprising titanium, zirconium, thorium, tin and. cerium, the steps comprising mixing a separately prepared solution containing a colloidal suspension of an oxide of the element with a solution containing a sulphate of the element, and heating the mixed solutions.

13. In the preparation of titanium oxide or hydroxide, the steps comprising adding a concentrated solution of titanium sulphate tof hot Water and cooling the mixed solution before any substantial precipitation of titanium dioxide takes place, mixing the resulting col- 7 v loidal solution with a solution containing titanium sulphate, and heating the mixed solution.

14. In a processof preparing a titanium oxygen compound the steps comprising mix; ing with agitation a solution of a hydrolyzable titanium salt with a separately prepared colloidal solution of a titanium oxygen compound and heating the mixed solution to effect precipitation.

15. I11 a process off-preparing a titanium oxygen compound the steps comprisingmixing with agitation a solution of hydrolyzable titanium salt with a separately preparedcolloidal solution of .a titanium oxygen compound in the presence of a substance adapted to serve as a constituent of a paint pigment.

16. A solution containing colloidal titanium dioxidecapable of passing through a filter and of being coagulated by boiling with hydrochloric acid.

In testimony whereof, I have signed my name to this specification this 12th. day of April, 1930.

JOSEPH BLUMENFE LD. 

